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DOI: 10.1055/a-2352-4902
A Homolytic Substitution Approach for Directing Group-Free Nickel-Catalyzed Dialkylation of Unactivated Alkenes
M.J.K. acknowledges funding support from the IMRE-NUS Chemistry joint collaboration project (A-8000301-00-00) and the Ministry of Education of Singapore Academic Research Fund Tier 2 (A-8000941-00-00).
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Abstract
The selective construction of two C(sp3)–C(sp3) bonds through trimolecular cross-coupling of unactivated alkenes remains one of the most difficult challenges in organic synthesis. Despite previous advances in metal-catalyzed coupling for the dicarbofunctionalization of alkenes, dialkylation is still problematic due to the instability of the requisite metal–alkyl intermediate, which undergoes facile β-hydride elimination or protodemetalation. Recently, our group was successful in developing a bimolecular homolytic substitution (SH2) strategy that circumvents metal–alkyl side reactions and accomplishes the challenging cross-coupling of metal–alkyl intermediates with alkyl radicals in the absence of a directing auxiliary, permitting a highly regioselective dialkylation of unactivated alkenes.
1 Introduction
2 Nickel-Catalyzed Dicarbofunctionalization of Unactivated Alkenes
3 Nickel-Catalyzed Dialkylation of Unactivated Alkenes
4 Conclusions and Perspectives
Key words
nickel catalysis - dialkylation - unactivated alkenes - bimolecular homolytic substitution - radicalsPublication History
Received: 28 May 2024
Accepted after revision: 25 June 2024
Accepted Manuscript online:
25 June 2024
Article published online:
15 July 2024
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For selected examples, see: